KR20240073017A - Photosensitive resin composition, photosensitive element, and method for producing a laminate - Google Patents

Abstract

It contains a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and a tetrazole compound, the content of the monomer unit of the styrene compound in the binder polymer exceeds 30% by mass, and the content of the tetrazole compound is in the binder polymer and A photosensitive resin composition containing 0.01 parts by mass or more based on a total of 100 parts by mass of the photopolymerizable compound.

Description

Photosensitive resin composition, photosensitive element, and method for producing a laminate

This disclosure relates to a photosensitive resin composition, a photosensitive element, a method for producing a laminate, etc.

In the manufacture of a laminate that can be used as a wiring board, a resist pattern is formed to obtain desired wiring. A resist pattern can be formed by exposing and developing a photosensitive resin layer obtained using a photosensitive resin composition. As a photosensitive resin composition, various compositions are being examined. For example, in Patent Document 1 below, a photosensitive resin composition containing an anthracene derivative is described.

Patent Document 1: International Publication No. 2007/004619

When forming a cured product pattern that can be used as a resist pattern using a photosensitive resin composition, a cured product pattern having a straight line portion and a straight space portion adjacent to the line portion may be formed. In such a cured product pattern, it may be required to obtain a cured product pattern having line portions and space portions formed without trouble while reducing the line width (width of the line portion).

In addition, according to the present inventor's knowledge, if the line width of a cured material pattern having a line portion and a space portion determined by microscopic observation to be formed without trouble is actually measured, the target line width and line width in the drawing pattern are Since there are cases where the actual measured values of Therefore, with respect to the photosensitive resin composition for obtaining a cured product pattern, it is required to obtain a cured product pattern having line portions and space portions formed without trouble while reducing the actual measured value of the line width.

One aspect of the present disclosure aims to provide a photosensitive resin composition capable of obtaining a cured pattern having line portions and space portions formed without trouble while reducing the actual measured value of the line width. Another aspect of the present disclosure aims to provide a photosensitive element using the photosensitive resin composition. Another aspect of the present disclosure aims to provide a method for manufacturing a laminate using the above-described photosensitive resin composition or the above-described photosensitive element.

[1] Containing a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and a tetrazole compound, the content of the monomer unit of the styrene compound in the binder polymer exceeds 30% by mass, and the tetrazole compound A photosensitive resin composition wherein the content is 0.01 parts by mass or more based on a total of 100 parts by mass of the binder polymer and the photopolymerizable compound.

[2] The photosensitive resin composition according to [1], wherein the content of the tetrazole compound is 0.01 to 1 part by mass based on a total of 100 parts by mass of the binder polymer and the photopolymerizable compound.

[3] The photosensitive resin composition according to [1] or [2], wherein the tetrazole compound contains 5-amino-1H-tetrazole.

[4] The photosensitive resin composition according to any one of [1] to [3], wherein the tetrazole compound contains 5-mercaptotetrazole.

[5] The photosensitive resin composition according to any one of [1] to [4], wherein the binder polymer has a weight average molecular weight of 30,000 to 40,000.

[6] The photosensitive resin composition according to any one of [1] to [5], wherein the photopolymerizable compound contains a bisphenol A type (meth)acrylic acid compound.

[7] The photosensitive resin composition according to any one of [1] to [6], which is a film.

[8] The photosensitive resin composition according to [7], wherein the photosensitive resin composition has a thickness of 30 μm or less.

[9] A photosensitive element comprising a support and a photosensitive resin layer disposed on the support, wherein the photosensitive resin layer contains the photosensitive resin composition according to any one of [1] to [8].

[10] A step of disposing a photosensitive resin layer on a substrate using the photosensitive resin composition according to any one of [1] to [8], or the photosensitive element according to [9], and a portion of the photosensitive resin layer. A method of manufacturing a laminate comprising a photocuring step and a step of removing an uncured portion of the photosensitive resin layer to form a cured product pattern.

According to one aspect of the present disclosure, a photosensitive resin composition capable of obtaining a cured pattern having line portions and space portions formed without trouble while reducing the actual measured value of the line width can be provided. According to another aspect of the present disclosure, a photosensitive element using the photosensitive resin composition can be provided. According to another aspect of the present disclosure, a method for manufacturing a laminate using the above-described photosensitive resin composition or the above-described photosensitive element can be provided. According to another aspect of the present disclosure, application of the photosensitive resin composition or photosensitive element to the formation of a resist pattern can be provided. According to another aspect of the present disclosure, application of the photosensitive resin composition or photosensitive element to the manufacture of a wiring board can be provided.

1 is a schematic cross-sectional view showing an example of a photosensitive element.
Figure 2 is a schematic diagram showing an example of a method for manufacturing a laminate.

Hereinafter, embodiments of the present disclosure will be described in detail.

In this specification, the numerical range indicated using “~” indicates a range that includes the numerical values written before and after “~” as the minimum and maximum values, respectively. “A or more” in a numerical range means A, and a range exceeding A. “A or less” in the numerical range means A and the range less than A. In the numerical range described in steps in this specification, the upper or lower limit of the numerical range at a certain level can be arbitrarily combined with the upper or lower limit of the numerical range at another level. In the numerical range described in this specification, the upper or lower limit of the numerical range may be replaced with the value shown in the examples. “A or B” may include either A or B, or may include both. Unless otherwise specified, the materials exemplified in this specification can be used individually or in combination of two or more types. The content of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified, when multiple substances corresponding to each component exist in the composition. The term "layer" includes not only the structure of the shape formed on the entire surface when observed in plan view, but also the structure of the shape formed on a part of the surface. The word "process" is included in this term not only as an independent process, but also when the intended effect of the process is achieved even if it cannot be clearly distinguished from other processes. “(meth)acrylate” means at least one of acrylate and the corresponding methacrylate. The same applies to other similar expressions such as “(meth)acrylic acid”. “Content of monomer units of (meth)acrylic acid” means the total amount of monomer units of acrylic acid and monomer units of methacrylic acid, and the same applies to other similar expressions. Unless otherwise specified, the “alkyl group” may be linear, branched, or cyclic.

In this specification, “EO modified” means a compound having a (poly)oxyethylene group. “PO modified” means a compound having a (poly)oxypropylene group. “EO·PO modified” means a compound having a (poly)oxyethylene group and a (poly)oxypropylene group. “(Poly)oxyethylene group” means at least one of an oxyethylene group and a polyoxyethylene group (a group in which two or more ethylene groups are linked by an ether bond). The same applies to other similar expressions such as “(poly)oxypropylene group”.

In this specification, “solid content of the photosensitive resin composition” refers to the non-volatile content excluding substances that may volatilize (water, organic solvent, etc.) in the photosensitive resin composition. That is, “solid content” refers to the component that remains without volatilizing when the photosensitive resin composition is dried, and also includes components such as liquid, starch syrup, and wax at room temperature (25°C).

<Photosensitive resin composition and cured product>

The photosensitive resin composition according to the present embodiment includes (A) a binder polymer (component (A)), (B) a photopolymerizable compound (component (B)), (C) a photopolymerization initiator (component (C)), (D) contains a tetrazole compound (component (D)), the content of the monomer unit of the styrene compound in component (A) exceeds 30% by mass, and the content of component (D) is in component (A) and (B) 0.01 parts by mass or more based on a total of 100 parts by mass of component. The photosensitive resin composition according to this embodiment can be used, for example, as a negative photosensitive resin composition. The photosensitive resin composition according to this embodiment may be in a liquid form or in a film form (photosensitive film).

The photosensitive resin composition according to this embodiment has photocurability, and a cured product can be obtained by photocuring the photosensitive resin composition. The cured product according to the present embodiment is a cured product (photocured product) of the photosensitive resin composition according to the present embodiment. The cured product according to the present embodiment may be in the form of a pattern (cured product pattern) or may be a resist pattern.

The thickness of the film-like photosensitive resin composition or the thickness of the cured product may be 1 μm or more, 5 μm or more, 10 μm or more, 15 μm or more, 20 μm or more, or 25 μm or more. The thickness of the film-like photosensitive resin composition or the thickness of the cured product may be 100 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, or 25 μm or less. From these viewpoints, the thickness of the film-like photosensitive resin composition or the thickness of the cured product may be 1 to 100 μm.

According to the photosensitive resin composition according to the present embodiment, a cured product pattern (cured product pattern with excellent adhesion; for example, a cured product pattern with excellent adhesion; for example, a cured product pattern having line portions and space portions formed without trouble while reducing the actual measured value of the line width formed cured material pattern) can be obtained. Regarding the factor for obtaining such an effect, the present inventors believe that component (D), which has a plurality of nitrogen atoms in the ring, promotes adhesion between the base material and the resin component of the cured product chemically (hydrogen bond, coordination bond, etc.) or It is assumed that the above-mentioned effects are achieved by providing physical assistance. However, the factors are not limited to the relevant content.

According to the photosensitive resin composition according to the present embodiment, in the case of forming a cured product pattern with a line width smaller than the space width, a cured product pattern having a line portion and a space portion is formed without trouble while reducing the actual measured value of the line width. can be obtained. According to the photosensitive resin composition according to the present embodiment, in the evaluation method described in the examples described later, after development, the space portion (unexposed portion) is removed without residue, and the line portion does not cause meandering or omission. The actual measured value of the line width in the cured product pattern formed without the method can be reduced to 7.00 μm or less.

The photosensitive resin composition according to the present embodiment contains a binder polymer (excluding the compound corresponding to the tetrazole compound) as the (A) component. Examples of the component (A) include acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, and phenol resin. Acrylic resin is a resin having a compound having a (meth)acryloyl group ((meth)acrylic acid compound) as a monomer unit, and includes styrene-based resin, epoxy-based resin, amide-based resin, amide-epoxy-based resin, Alkyd resins and phenolic resins belong to acrylic resins.

The component (A) may contain an acrylic resin from the viewpoint of easily reducing the actual measured value of the line width. From the viewpoint of easily reducing the actual measured value of the line width, the content of the acrylic resin is 50% by mass or more, more than 50% by mass, 70% by mass or more, 90% by mass or more, based on the total mass of component (A). It may be 95 mass% or more, 98 mass% or more, 99 mass% or more, or substantially 100 mass% (an aspect in which component (A) substantially consists of acrylic resin).

Examples of compounds having a (meth)acryloyl group include (meth)acrylic acid and (meth)acrylic acid ester. As (meth)acrylic acid ester, (meth)acrylic acid alkyl ((meth)acrylic acid alkyl ester, excluding compounds corresponding to (meth)acrylic acid cycloalkyl), (meth)acrylic acid cycloalkyl ((meth)acrylic acid cycloalkyl ester) , aryl (meth)acrylic acid ((meth)acrylic acid aryl ester), (meth)acrylamide compounds (diacetone acrylamide, etc.), (meth)acrylic acid glycidyl ester, and styryl (meth)acrylic acid.

Component (A) may have (meth)acrylic acid as a monomer unit from the viewpoint of easily reducing the actual measured value of the line width.

When component (A) has (meth)acrylic acid as a monomer unit, the content of the monomer unit of (meth)acrylic acid is the total amount of monomer units constituting component (A) from the viewpoint of easily reducing the actual measured value of the line width. It may be within the following range based on . The content of the monomer unit of (meth)acrylic acid may be 1% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, or 27% by mass or more. The content of the monomer unit of (meth)acrylic acid may be 50 mass% or less, less than 50 mass%, 45 mass% or less, 40 mass% or less, 35 mass% or less, 30 mass% or less, or 27 mass% or less. From these viewpoints, the content of the monomer unit of (meth)acrylic acid may be 1 to 50 mass%.

Component (A) may have alkyl (meth)acrylate as a monomer unit from the viewpoint of easily reducing the actual measured value of the line width. Examples of the alkyl group of alkyl (meth)acrylate include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, etc., and the alkyl group is , various structural isomers may be used. The number of carbon atoms of the alkyl group of alkyl (meth)acrylate may be 1 to 4, 1 to 3, 2 to 3, or 1 to 2 from the viewpoint of easily reducing the actual measured value of the line width.

The alkyl group of alkyl (meth)acrylate may have a substituent. Examples of the substituent include hydroxy group, amino group, epoxy group, furyl group, halogeno group (fluoro group, chloro group, bromo group, etc.). Examples of alkyl (meth)acrylate include hydroxyalkyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, and (meth)acrylate. ) Acrylic acid 2,2,3,3-tetrafluoropropyl, α-chloro(meth)acrylic acid, α-bromo(meth)acrylic acid, etc.

Component (A) may have hydroxyalkyl (meth)acrylate as a monomer unit from the viewpoint of easily reducing the actual measured value of the line width. Examples of hydroxyalkyl (meth)acrylate include hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, ( Meth) hydroxyhexyl acrylate, etc. can be mentioned.

Content of alkyl (meth)acrylate monomer units when component (A) has alkyl (meth)acrylate as a monomer unit, or when component (A) has hydroxyalkyl (meth)acrylate as a monomer unit The content of the monomer unit of hydroxyalkyl (meth)acrylate may be within the following range based on the total amount of monomer units constituting component (A) from the viewpoint of easily reducing the actual measured value of the line width. The content of the above-mentioned monomer units may be 0.1 mass% or more, 0.5 mass% or more, 1 mass% or more, 2 mass% or more, or 3 mass% or more. The content of the above-mentioned monomer units may be 20 mass% or less, 15 mass% or less, 10 mass% or less, 8 mass% or less, 5 mass% or less, or 3 mass% or less. From these viewpoints, the content of the above-mentioned monomer units may be 0.1 to 20 mass%.

Component (A) may have aryl (meth)acrylate as a monomer unit from the viewpoint of easily reducing the actual measured value of the line width. Examples of aryl (meth)acrylate include benzyl (meth)acrylate, phenyl (meth)acrylate, and naphthyl (meth)acrylate.

When component (A) has aryl (meth)acrylate as a monomer unit, the content of the aryl (meth)acrylate monomer unit is determined by the monomer unit constituting component (A) from the viewpoint of easily reducing the actual measured value of the line width. The range below may be based on the total amount. The content of the monomer unit of aryl (meth)acrylate may be 1% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, or 20% by mass or more. The content of the monomer unit of aryl (meth)acrylate is 50 mass% or less, less than 50 mass%, 45 mass% or less, 40 mass% or less, 35 mass% or less, 30 mass% or less, 25 mass% or less, or 20 mass% or less. It may be less than % by mass. From these viewpoints, the content of the monomeric unit of aryl (meth)acrylate may be 1 to 50 mass%.

(A) Component has a styrene compound as a monomer unit. Examples of styrene compounds include styrene and styrene derivatives. Examples of styrene derivatives include vinyltoluene and α-methylstyrene. Component (A) may have hydroxyalkyl (meth)acrylate and a styrene compound as monomer units from the viewpoint of easily reducing the actual measured value of the line width.

The content of the monomer unit of the styrene compound exceeds 30% by mass based on the total amount of monomer units constituting component (A), and from the viewpoint of easily reducing the actual measured value of the line width, it may be within the range below. do. The content of the monomer unit of the styrene compound may be 32% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 47% by mass or more, or 50% by mass or more. The content of the monomer unit of the styrene compound is 90 mass% or less, 85 mass% or less, 80 mass% or less, 75 mass% or less, 70 mass% or less, 65 mass% or less, 60 mass% or less, 55 mass% or less, Alternatively, it may be 50% by mass or less. From these viewpoints, the content of the monomer unit of the styrene compound may exceed 30 mass% and may be 90 mass% or less.

(A) Component may have other monomers as monomer units. Examples of such monomers include vinyl alcohol ethers (vinyl-n-butyl ether, etc.), (meth)acrylonitrile, maleic acid, maleic anhydride, maleic acid monoester (monomethyl maleate, monoethyl maleate) , monoisopropyl maleate, etc.), fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid, etc.

The acid value of component (A) may be within the following range from the viewpoint of easily reducing the actual measured value of the line width. (A) The acid value of the component is 80 mgKOH/g or more, 90 mgKOH/g or more, 100 mgKOH/g or more, more than 100 mgKOH/g, 120 mgKOH/g or more, 140 mgKOH/g or more, 150 mgKOH/g or more, 160 mgKOH/g or more, It may be more than 170mgKOH/g. The acid value of the component (A) may be 250 mgKOH/g or less, 240 mgKOH/g or less, 230 mgKOH/g or less, 210 mgKOH/g or less, 200 mgKOH/g or less, or 180 mgKOH/g or less. From these viewpoints, the acid value of component (A) may be 80 to 250 mgKOH/g. The acid value of component (A) can be adjusted depending on the content of the monomer unit (for example, the monomer unit of (meth)acrylic acid) constituting component (A). (A) The acid value of component can be measured by the method described in the Examples. When the measurement object is a solution obtained by mixing component (A) with volatile components such as a synthetic solvent or dilution solvent, the acid value can be calculated using the following formula. When mixing component (A) with volatile components such as synthetic solvents or diluting solvents, heat the components for 1 to 4 hours at a temperature at least 10°C higher than the boiling point of the volatile components before accurately weighing them. The acid value can also be measured after removing the volatile matter.

Acid value=0.1×Vf×56.1/(Wp×I/100)

[Wherein, Vf represents the appropriate amount (unit: mL) of KOH (potassium hydroxide) aqueous solution, Wp represents the mass (unit: g) of the solution containing the component (A) to be measured, and I represents the measurement It represents the ratio (unit: mass%) of non-volatile matter in the solution containing the target component (A).]

The weight average molecular weight (Mw) of component (A) may be within the following range from the viewpoint of easily reducing the actual measured value of the line width. The weight average molecular weight of component (A) may be 10,000 or more, 20,000 or more, 25,000 or more, 30,000 or more, or 35,000 or more. The weight average molecular weight of component (A) may be 100,000 or less, 80,000 or less, 70,000 or less, 70,000 or less, 65,000 or less, 60,000 or less, 50,000 or less, 40,000 or less, or 35,000 or less. From these viewpoints, the weight average molecular weight of component (A) may be 10,000 to 100,000, 20,000 to 50,000, or 30,000 to 40,000.

The number average molecular weight (Mn) of component (A) may be within the following range from the viewpoint of easily reducing the actual measured value of the line width. The number average molecular weight of the component (A) may be 5000 or more, 10000 or more, 12000 or more, 15000 or more, or 16000 or more. The number average molecular weight of component (A) may be 50,000 or less, 40,000 or less, 35,000 or less, 30,000 or less, 25,000 or less, 20,000 or less, or 16,000 or less. From these viewpoints, the number average molecular weight of component (A) may be 5000 to 50000, 10000 to 25000, or 15000 to 20000.

The dispersion degree (weight average molecular weight/number average molecular weight) of component (A) may be within the following range from the viewpoint of easily reducing the actual measured value of the line width. (A) The dispersion degree of component may be 1.0 or more, 1.5 or more, 1.8 or more, 2.0 or more, or 2.1 or more. The dispersion degree of component (A) may be 3.0 or less, 2.8 or less, 2.5 or less, 2.3 or less, or 2.2 or less. From these viewpoints, the dispersion degree of component (A) may be 1.0 to 3.0.

The weight average molecular weight and number average molecular weight can be measured, for example, by gel permeation chromatography (GPC) using a calibration curve of standard polystyrene. More specifically, it can be measured under the conditions described in the examples. For compounds with low molecular weight, if it is difficult to measure the weight average molecular weight and number average molecular weight using the above-mentioned measurement methods, the molecular weight may be measured by another method and the average value may be calculated.

The content of component (A) may be within the following range based on the total solid content of the photosensitive resin composition from the viewpoint of easily reducing the actual measured value of the line width. The content of component (A) may be 10 mass% or more, 20 mass% or more, 30 mass% or more, 40 mass% or more, 45 mass% or more, or 50 mass% or more from the viewpoint of excellent film formability. . The content of component (A) may be 90 mass% or less, 80 mass% or less, 75 mass% or less, 70 mass% or less, 65 mass% or less, 60 mass% or less, or 55 mass% or less. From these viewpoints, the content of component (A) may be 10 to 90 mass%.

The content of component (A) may be within the following range with respect to 100 parts by mass of the total amount of component (A) and component (B) from the viewpoint of easily reducing the actual measured value of the line width. The content of component (A) is, from the viewpoint of excellent film formability, 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, 40 parts by mass or more, 45 parts by mass or more, 50 parts by mass or more, or 55 parts by mass or more. It may be more than parts by mass. The content of component (A) may be 90 parts by mass or less, 80 parts by mass or less, 75 parts by mass or less, 70 parts by mass or less, 65 parts by mass or less, or 60 parts by mass or less. From these viewpoints, the content of component (A) may be 10 to 90 mass.

The photosensitive resin composition according to the present embodiment contains a photopolymerizable compound (excluding the compound corresponding to the tetrazole compound) as the (B) component. The photopolymerizable compound is a compound that is polymerized by light, and may be, for example, a compound having an ethylenically unsaturated bond.

(B) Components include bisphenol A-type (meth)acrylic acid compound, EO-modified di(meth)acrylate, PO-modified di(meth)acrylate, EO·PO-modified di(meth)acrylate, and polyalkylene glycol diacrylate. (meth)acrylate (polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, etc.), EO modified polyalkylene glycol di(meth)acrylate, PO modified polyalkylene glycol Lycol di(meth)acrylate, EO·PO modified polyalkylene glycol di(meth)acrylate, trimethylol propane di(meth)acrylate, trimethylol propane tri(meth)acrylate, EO Modified trimethylolpropane tri(meth)acrylate, PO modified trimethylolpropane tri(meth)acrylate, EO·PO modified trimethylolpropane tri(meth)acrylate, ditrimethylolpropane skeleton Compounds having, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, EO modified pentaerythritol tetra(meth)acrylate, PO modified pentaerythritol tetra(meth)acrylate Rate, EO·PO modified pentaerythritol tetra(meth)acrylate, EO modified dipentaerythritol hexa(meth)acrylate, PO modified dipentaerythritol hexa(meth)acrylate, EO·PO modified dipentaerythritol Hexa(meth)acrylate, nonylphenoxypolyethyleneoxyacrylate, phthalic acid-based compounds, alkyl (meth)acrylate, photopolymerizable compounds (oxetane compounds, etc.) having at least one cationically polymerizable cyclic ether group in the molecule. You can.

The component (B) may contain a bisphenol A (meth)acrylic acid compound from the viewpoint of easily reducing the actual measured value of the line width. As bisphenol A type (meth)acrylic acid compounds, 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane(2,2-bis(4-((meth)acryloxypentaethoxy) )phenyl)propane, etc.), 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolybutoxy)phenyl )propane, 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane, etc. Component (B) may contain 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane from the viewpoint of easily reducing the actual measured value of the line width, and 2,2-bis (4-((meth)acryloxypentaethoxy)phenyl)propane may be included.

The content of the bisphenol A type (meth)acrylic acid compound is 100% by mass or less based on the total mass of component (B), and may be within the following range from the viewpoint of easily reducing the actual measured value of the line width. The content of bisphenol A type (meth)acrylic acid compound is 50% by mass or more, more than 50% by mass, 60% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, 85% by mass or more, or 90% by mass. It may be more than mass%. The content of the bisphenol A type (meth)acrylic acid compound may be less than 100 mass%, 99 mass% or less, 98 mass% or less, 97 mass% or less, 95 mass% or less, 92 mass% or less, or 91 mass% or less. . From these viewpoints, the content of the bisphenol A type (meth)acrylic acid compound may be 50 to 100 mass%.

The content of the bisphenol A type (meth)acrylic acid compound may be within the following range based on the total solid content of the photosensitive resin composition from the viewpoint of easily reducing the actual measured value of the line width. The content of the bisphenol A type di(meth)acrylic acid compound is 1% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, or, It may be 35% by mass or more. The content of bisphenol A type (meth)acrylic acid compound is 90 mass% or less, 80 mass% or less, 70 mass% or less, 65 mass% or less, 60 mass% or less, 55 mass% or less, 50 mass% or less, 45 mass% or less. It may be less than or equal to 40% by mass. From these viewpoints, the content of the bisphenol A type (meth)acrylic acid compound may be 1 to 90 mass%.

The content of the bisphenol A type (meth)acrylic acid compound may be within the following range with respect to 100 parts by mass of the total amount of component (A) and component (B) from the viewpoint of easily reducing the actual measured value of the line width. The content of the bisphenol A type (meth)acrylic acid compound is 1 part by mass or more, 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, 32 parts by mass or more. Above, it may be 35 parts by mass or more, 38 parts by mass or more, or 40 parts by mass or more. The content of the bisphenol A type (meth)acrylic acid compound may be 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, 45 parts by mass or less, or 40 parts by mass or less. . From these viewpoints, the content of the bisphenol A type (meth)acrylic acid compound may be 1 to 90 mass.

The content of component (B) may be in the following range based on the total solid content of the photosensitive resin composition from the viewpoint of easily reducing the actual measured value of the line width. The content of component (B) may be 10 mass% or more, 15 mass% or more, 20 mass% or more, 25 mass% or more, 30 mass% or more, 35 mass% or more, or 40 mass% or more. (B) The content of component may be 90 mass% or less, 80 mass% or less, 70 mass% or less, 65 mass% or less, 60 mass% or less, 55 mass% or less, 50 mass% or less, or 45 mass% or less. do. From these viewpoints, the content of component (B) may be 10 to 90 mass%.

The content of component (B) may be within the following range with respect to 100 parts by mass of the total amount of component (A) and component (B) from the viewpoint of easily reducing the actual measured value of the line width. The content of component (B) may be 10 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, or 40 parts by mass or more. The content of component (B) may be 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 60 parts by mass or less, 55 parts by mass or less, 50 parts by mass or less, or 45 parts by mass or less. From these viewpoints, the content of component (B) may be 10 to 90 parts by mass.

The photosensitive resin composition according to the present embodiment contains a photopolymerization initiator (excluding the compound corresponding to the tetrazole compound) as the (C) component.

(C) As a component, hexaarylbiimidazole compound; Benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1- [4-(4-morpholinyl)phenyl]-1-butanone, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)ketone, 2-methyl-1-[4 Aromatic ketones such as -(methylthio)phenyl]-2-morpholino-propanone-1; Quinone compounds such as alkylanthraquinone; Benzoin ether compounds such as benzoin alkyl ether; Benzoin compounds such as benzoin and alkylbenzoin; Benzyl derivatives such as benzyl dimethyl ketal; Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; Bis(2,6-dimethylbenzoyl)-2,4,4-trimethyl-pentylphosphine oxide; (2,4,6-trimethylbenzoyl)ethoxyphenylphosphine oxide, etc. can be mentioned.

Component (C) may contain a hexaarylbiimidazole compound from the viewpoint of easily reducing the actual measured value of the line width. The aryl group in the hexaarylbiimidazole compound may be a phenyl group or the like. The hydrogen atom bonded to the aryl group in the hexaarylbiimidazole compound may be substituted with a halogen atom (chlorine atom, etc.).

The hexaarylbiimidazole compound may be a 2,4,5-triarylimidazole dimer. Examples of 2,4,5-triarylimidazole dimer include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer and 2-(o-chlorophenyl)-4,5-bis. -(m-methoxyphenyl)imidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, etc. The hexaarylbiimidazole compound may contain a 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer from the viewpoint of easily reducing the actual measured value of the line width, and 2,2'- It may also contain bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

The content of the hexaarylbiimidazole compound is 50% by mass or more, more than 50% by mass, 70% by mass or more, 90% by mass, based on the total amount of component (C), from the viewpoint of easily reducing the actual measured value of the line width. % or more, 95 mass % or more, 98 mass % or more, 99 mass % or more, or substantially 100 mass % (an embodiment in which component (C) substantially consists of a hexaarylbiimidazole compound).

The content of component (C) may be within the following range based on the total solid content of the photosensitive resin composition from the viewpoint of easily reducing the actual measured value of the line width. (C) The content of component may be 0.1 mass% or more, 0.5 mass% or more, 1 mass% or more, 2 mass% or more, 3 mass% or more, 4 mass% or more, 5 mass% or more, or 5.5 mass% or more. do. The content of component (C) may be 20 mass% or less, 15 mass% or less, 12 mass% or less, 10 mass% or less, 8 mass% or less, 7 mass% or less, or 6 mass% or less. From these viewpoints, the content of component (C) may be 0.1 to 20 mass%.

The content of component (C) may be within the following range with respect to 100 parts by mass of the total amount of component (A) and component (B) from the viewpoint of easily reducing the actual measured value of the line width. (C) The content of component is 0.1 parts by mass or more, 0.5 parts by mass or more, 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, 4 parts by mass or more, 5 parts by mass or more, 5.5 parts by mass or more, or, It may be 6 parts by mass or more. The content of component (C) may be 20 parts by mass or less, 15 parts by mass or less, 12 parts by mass or less, 10 parts by mass or less, 8 parts by mass or less, 7 parts by mass or less, or 6 parts by mass or less. From these viewpoints, the content of component (C) may be 0.1 to 20 mass.

The photosensitive resin composition according to this embodiment contains a tetrazole compound (a compound having a tetrazole ring) as the (D) component. As the component (D), a compound represented by the following general formula (1) can be used.

[Formula 1]

[In formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group (substituted or unsubstituted alkyl group; excluding cycloalkyl groups), a cycloalkyl group (substituted or unsubstituted cycloalkyl group), or a phenyl group. (Substituted or unsubstituted phenyl group), amino group, mercapto group, or benzoyl group. R ¹ and R ² may be combined with each other to form a cyclic structure.]

The number of carbon atoms of the alkyl group may be 1 to 20, 1 to 16, 1 to 12, 1 to 8, 1 to 6, 1 to 4, 1 to 3, or 1 to 2. The number of carbon atoms of the cycloalkyl group may be 3 to 10, or 3 to 6. Substituents for alkyl groups and cycloalkyl groups include halogeno groups (e.g. fluoro groups), amino groups, monoalkylamino groups, dialkylamino groups, mercapto groups, carboxy groups, carboxylate groups, hydroxy groups, alkoxy groups, aldehyde groups, etc. I can hear it. Examples of substituents for the phenyl group include alkyl group, halogeno group (e.g. fluoro group), amino group, monoalkylamino group, dialkylamino group, mercapto group, carboxy group, carboxylate group, hydroxy group, alkoxy group, aldehyde group, etc. You can.

(D) Components include 1H-tetrazole, 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole, 5-(2-aminophenyl)-1H-tetrazole, and 5-phenyl-1H-tetra. Sol, 5-mercapto-1H-tetrazole, 1-methyl-5-ethyltetrazole, 1-methyl-5-aminotetrazole, 1-methyl-5-mercaptotetrazole, 1-methyl-5-benzoyl -1H-tetrazole, 1-carboxymethyl-5-amino-tetrazole, 1-cyclohexyl-5-mercaptotetrazole, 1-phenyltetrazole, 1-phenyl-5-mercaptotetrazole, 1-carboxy Methyl-5-mercaptotetrazole, 1,5-pentamethylenetetrazole, 1-(2-dimethylaminoethyl)-5-mercaptotetrazole, 2-methoxy-5-(5-trifluoromethyl -1H-tetrazol-1-yl)-benzaldehyde, etc. can be mentioned. The component (D) may contain at least one member selected from the group consisting of 5-amino-1H-tetrazole and 5-mercaptotetrazole from the viewpoint of easily reducing the actual measured value of the line width. That is, component (D) may be in a form containing 5-amino-1H-tetrazole or may be in a form containing 5-mercaptotetrazole.

The content of component (D) may be in the following range based on the total solid content of the photosensitive resin composition from the viewpoint of easily reducing the actual measured value of the line width. (D) The content of the component is 0.01 mass% or more, 0.05 mass% or more, 0.1 mass% or more, 0.15 mass% or more, 0.2 mass% or more, 0.25 mass% or more, 0.3 mass% or more, 0.35 mass% or more, 0.4 mass% or more. % or more, or may be 0.45 mass% or more. (D) The content of component is 5 mass% or less, 3 mass% or less, 1 mass% or less, 0.9 mass% or less, 0.8 mass% or less, 0.7 mass% or less, 0.6 mass% or less, 0.55 mass% or less, or, It may be 0.5% by mass or less. From these viewpoints, the content of component (D) may be 0.01 to 5 mass%.

The content of component (D) may be within the following range with respect to 100 parts by mass of the total amount of component (A) and component (B) from the viewpoint of easily reducing the actual measured value of the line width. (D) The content of component is 0.01 part by mass or more, 0.05 part by mass or more, 0.1 part by mass or more, 0.15 part by mass or more, 0.2 part by mass or more, 0.25 part by mass or more, 0.3 part by mass or more, 0.35 part by mass or more, 0.4 mass part or more. parts or more, 0.45 parts by mass or more, or 0.5 parts by mass or more. The content of component (D) is 5 parts by mass or less, 3 parts by mass or less, 1 part by mass or less, 0.9 parts by mass or less, 0.8 parts by mass or less, 0.7 parts by mass or less, 0.6 parts by mass or less, 0.55 parts by mass or less, or, It may be 0.5 parts by mass or less. From these viewpoints, the content of component (D) may be 0.01 to 5 parts by mass, or 0.01 to 1 part by mass.

The photosensitive resin composition according to this embodiment may contain other components (excluding the compounds corresponding to (A) component, (B) component, (C) component, or (D) component). Other components include hydrogen donors, anthracene compounds, polymerization inhibitors, organic solvents, dyes (malachite green, etc.), photosensitizers (excluding anthracene compounds), tribromophenyl sulfone, photochromic agents, thermochromic inhibitors, plasticizers ( p-toluenesulfonamide, etc.), pigments, fillers, anti-foaming agents, flame retardants, stabilizers (light stabilizers, etc.), adhesion imparting agents, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, heat cross-linking agents, etc.

Examples of the hydrogen donor include bis[4-(dimethylamino)phenyl]methane, bis[4-(diethylamino)phenyl]methane, leuco crystal violet, and N-phenylglycine.

The content of the hydrogen donor may be within the following range with respect to 100 parts by mass of the total amount of component (A) and component (B) from the viewpoint of easily reducing the actual measured value of the line width. The content of the hydrogen donor may be 0.1 part by mass or more, 0.2 part by mass or more, 0.3 part by mass or more, 0.4 part by mass or more, or 0.5 part by mass or more. The content of the hydrogen donor may be 5 parts by mass or less, 3 parts by mass or less, 2 parts by mass or less, 1.5 parts by mass or less, 1 part by mass or less, 0.8 parts by mass or less, 0.7 parts by mass or less, or 0.5 parts by mass or less. From these viewpoints, the content of the hydrogen donor may be 0.1 to 5 mass.

Examples of anthracene compounds include 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, and 9,10-diethoxyanthracene. The anthracene compound may contain 9,10-dibutoxyanthracene from the viewpoint of easily reducing the actual measured value of the line width.

The content of the anthracene compound may be within the following range with respect to 100 parts by mass of the total amount of component (A) and component (B) from the viewpoint of easily reducing the actual measured value of the line width. The content of the anthracene compound may be 0.1 parts by mass or more, 0.2 parts by mass or more, 0.3 parts by mass or more, 0.4 parts by mass or more, 0.5 parts by mass or more, 0.6 parts by mass or more, or 0.65 parts by mass or more. The content of the anthracene compound may be 5 parts by mass or less, 3 parts by mass or less, 2 parts by mass or less, 1.5 parts by mass or less, 1 part by mass or less, 0.8 parts by mass or less, or 0.7 parts by mass or less. From these viewpoints, the content of the anthracene compound may be 0.1 to 5 mass.

The polymerization inhibitor suppresses polymerization in the unexposed portion during resist pattern formation and tends to improve resolution. As a polymerization inhibitor, t-butylcatechol (e.g., 4-t-butylcatechol), hindered amine (e.g., 2,2,6,6-tetramethyl-4-hydroxypiperidine-1) -oxyl), 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, etc.

The content of the polymerization inhibitor may be within the following range with respect to 100 parts by mass of the total amount of component (A) and component (B). From the viewpoint of easily obtaining excellent sensitivity and resolution, the content of the polymerization inhibitor is 0.001 parts by mass or more, 0.003 parts by mass or more, 0.005 parts by mass or more, 0.01 parts by mass or more, 0.015 parts by mass or more, 0.02 parts by mass or more, or, It may be 0.025 parts by mass or more. The content of the polymerization inhibitor may be 0.1 part by mass or less, 0.05 part by mass or less, 0.04 part by mass or less, or 0.03 part by mass or less from the viewpoint of easily obtaining excellent sensitivity and adhesion. From these viewpoints, the content of the polymerization inhibitor may be 0.001 to 0.1 mass.

Examples of organic solvents include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, propylene glycol monomethyl ether, and the like.

The photosensitive resin composition according to the present embodiment does not need to contain at least one selected from the group consisting of a benzotriazole compound and an aliphatic diamine compound having 8 to 30 carbon atoms. The content of the benzotriazole compound or the content of the aliphatic diamine compound having 8 to 30 carbon atoms may be 0.001% by mass or less, less than 0.001% by mass, or 0.0001% by mass or less, based on the total solid content of the photosensitive resin composition. It may be 0% by mass.

<Photosensitive element>

The photosensitive element according to the present embodiment includes a support and a photosensitive resin layer disposed on the support, and the photosensitive resin layer contains the photosensitive resin composition according to the present embodiment. The photosensitive element according to this embodiment may be provided with a protective layer disposed on the photosensitive resin layer. The photosensitive element according to this embodiment may be provided with a cushion layer, an adhesive layer, a light absorption layer, a gas barrier layer, etc. The photosensitive element may be in the form of a sheet or may be in the form of a photosensitive element roll wound around a core.

1 is a schematic cross-sectional view showing an example of a photosensitive element. As shown in FIG. 1, the photosensitive element 1 includes a support (support film) 2, a photosensitive resin layer 3 disposed on the support 2, and a photosensitive resin layer 3 disposed on the photosensitive resin layer 3. It is provided with a protective layer (protective film) 4. The photosensitive resin layer 3 consists of the photosensitive resin composition according to this embodiment.

The photosensitive element 1 can be obtained, for example, by the following procedure. First, a photosensitive resin layer (3) is formed on the support (2). The photosensitive resin layer 3 can be formed, for example, by drying an application layer formed by applying a photosensitive resin composition containing an organic solvent. Next, the protective layer (4) is disposed on the photosensitive resin layer (3).

Each of the support and the protective layer may be a polymer film having heat resistance and solvent resistance, and may be a polyester film (polyethylene terephthalate film, etc.), a polyolefin film (polyethylene film, polypropylene film, etc.), or a hydrocarbon-based polymer (polyolefin film, etc.). excluded), etc. The type of film constituting the protective layer and the type of film constituting the support may be the same or different from each other.

The thickness of the support may be 1 μm or more, 5 μm or more, 10 μm or more, or 15 μm or more from the viewpoint of easily suppressing breakage of the support when peeling the support from the photosensitive resin layer. The thickness of the support may be 100 μm or less, 50 μm or less, 30 μm or less, or 20 μm or less from the viewpoint of easy exposure when exposing through the support. The thickness of the photosensitive resin layer (thickness after drying; when the photosensitive resin composition contains an organic solvent, the thickness after volatilizing the organic solvent) may be the thickness of the film-like photosensitive resin composition described above.

<Method for manufacturing laminate>

The method for manufacturing a laminate according to the present embodiment includes a photosensitive resin layer disposition step of disposing the photosensitive resin layer on a base material (for example, a substrate) using the photosensitive resin composition or photosensitive element according to the present embodiment, and photosensitive water. It includes an exposure process to photocure (expose) a portion of the base layer, and a development process to form a cured product pattern by removing the uncured portion (unexposed portion) of the photosensitive resin layer. The laminated body according to the present embodiment is obtained by the manufacturing method of the laminated body according to the present embodiment, and may be a wiring board (for example, a printed wiring board). The laminate according to the present embodiment may be provided with a base material and a cured product pattern (cured product according to the present embodiment) disposed on the base material.

In the photosensitive resin layer arrangement process, the photosensitive resin layer consisting of the photosensitive resin composition according to this embodiment is disposed on the base material. For example, the photosensitive resin layer may be formed by applying and drying the photosensitive resin composition on a substrate, or may be formed by removing the protective layer from the photosensitive element and then pressing the photosensitive resin layer of the photosensitive element to the substrate while heating.

In the exposure process, actinic light may be irradiated with a mask placed on the photosensitive resin layer, and areas of the photosensitive resin layer other than the area where the mask is placed may be exposed and photocured. LDI may be performed without using a mask. A part of the photosensitive resin layer may be exposed and photocured by irradiating actinic light in a desired pattern using a direct drawing exposure method such as an exposure method or a DLP exposure method. As a light source of actinic light, an ultraviolet light source or a visible light source may be used, such as a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a gas laser (argon laser, etc.), or a solid-state laser (YAG laser, etc.). , semiconductor lasers, etc.

The development method in the development process may be, for example, wet development or dry development. Wet development can be performed using a developer corresponding to the photosensitive resin composition, for example, by a method such as a dip method, a puddle method, a spray method, brushing, slapping, scrubbing, or shaking immersion. The developing solution is appropriately selected depending on the structure of the photosensitive resin composition, and may be an alkaline developing solution or an organic solvent developing solution.

Alkaline developers include alkali hydroxides such as hydroxide of lithium, sodium, or potassium; Alkali carbonates such as carbonates or bicarbonates of lithium, sodium, potassium or ammonium; Alkali metal phosphates such as potassium phosphate and sodium phosphate; Alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; borax; sodium metasilicate; tetramethylammonium hydroxide; Ethanolamine; ethylenediamine; diethylenetriamine; 2-amino-2-hydroxymethyl-1,3-propanediol; 1,3-diamino-2-propanol; It may be an aqueous solution containing a base such as morpholine.

The organic solvent developer is an organic solvent such as 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. It may be contained.

The method for manufacturing a laminate according to the present embodiment includes curing the photosensitive resin layer by performing heating at 60 to 250° C. or exposure at 0.2 to 10 J/cm ² after the exposure process and/or the development process. A process for further hardening the part may be provided.

The method for manufacturing a laminate according to the present embodiment may include, after the development process, a metal layer forming step of forming a metal layer on at least a portion of the portion of the substrate where the cured product pattern is not formed. The metal layer may be, for example, a metallic copper layer. The metal layer can be formed, for example, by performing plating treatment. The plating treatment may be one or both of electrolytic plating treatment and electroless plating treatment. The laminate according to the present embodiment may be provided with a base material, a cured product pattern disposed on the substrate, and a metal layer disposed on at least a portion of the portion of the substrate where the cured product pattern is not formed.

The method for manufacturing a laminate according to the present embodiment may include a step of removing the cured product pattern after the metal layer forming step. The cured product pattern can be removed, for example, by performing development using a strong alkaline aqueous solution, such as an immersion method or a spray method.

Figure 2 is a schematic diagram showing an example of a method for manufacturing a laminated body (method for manufacturing a wiring board). In an example of a method for manufacturing a laminate, first, as shown in Figure 2 (a), a base material (for example, For example, a substrate for circuit formation) (10) is prepared. The conductor layer 10b may be, for example, a metallic copper layer.

Next, as shown in FIG. 2(b), the photosensitive resin layer 12 is disposed on the conductor layer 10b of the substrate 10 (photosensitive resin layer disposition step). In the photosensitive resin layer arrangement process, the photosensitive resin layer 12 is disposed on the conductor layer 10b of the base material 10 using the photosensitive resin composition or photosensitive element according to the present embodiment.

Next, as shown in FIG. 2(c), actinic light L is irradiated with the mask 14 disposed on the photosensitive resin layer 12, and the mask 14 in the photosensitive resin layer 12 is irradiated. The area other than the area where is placed is exposed and photocured.

Next, after removing the mask 14, as shown in (d) of FIG. 2, areas other than the photocured portion (uncured portion) in the photosensitive resin layer are removed from the substrate 10 by development, and A resist pattern 12a consisting of a flowering portion (cured product of the photosensitive resin layer) is formed.

Next, as shown in FIG. 2(e), a wiring layer (metal layer) 16 is formed in a portion of the conductor layer 10b of the substrate 10 where the resist pattern 12a is not formed. The wiring layer 16 may be formed of the same material as the conductor layer 10b, or may be formed of a different material.

Next, as shown in FIG. 2(f), the resist pattern 12a is removed and the conductor layer 10b provided at a position corresponding to the resist pattern 12a is removed to form the conductor layer 10c. do. As a result, a wiring board 18 is obtained including the conductor layer 10c and the wiring layer 16 disposed on the insulating layer 10a. The conductor layer 10b can be removed by etching. The etching solution is appropriately selected depending on the type of the conductor layer 10b, and may be, for example, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, or a hydrogen peroxide etching solution.

Example

Hereinafter, the present disclosure will be described in more detail through examples, but the present disclosure is not limited to these examples.

<Synthesis of binder polymer>

A solution (a) was prepared by mixing 27 parts by mass of methacrylic acid, 3 parts by mass of 2-hydroxyethyl methacrylate, 20 parts by mass of benzyl methacrylate, 50 parts by mass of styrene, and 0.9 parts by mass of azobisisobutyronitrile. ) was prepared. Solution (b) was prepared by dissolving 0.5 parts by mass of azobisisobutyronitrile in 50 parts by mass of a mixed solution of 30 parts by mass of methyl cellosolve and 20 parts by mass of toluene. After adding 500 g of a mixed solution of 30 parts by mass of methyl cellosolve and 20 parts by mass of toluene to a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel, and nitrogen gas introduction tube, the mixture was stirred while spraying nitrogen gas into the flask, The temperature was raised to ℃. After the solution (a) was dropped into the flask described above for 4 hours at a constant dropping rate, the solution in the flask was stirred at 80°C for 2 hours. Next, solution (b) was dropped into the flask described above for 10 minutes at a constant dropping rate, and then the solution in the flask was stirred at 80°C for 3 hours. Additionally, the solution in the flask was heated to 90°C for 30 minutes and then kept at 90°C for 2 hours. After that, stirring was stopped and the solution was cooled to room temperature (25°C) to obtain a binder polymer solution. The non-volatile content (solid content) of the binder polymer solution was 56% by mass.

The acid value of the binder polymer was 176 mgKOH/g. The acid value was measured in the following procedure. First, 1 g of the binder polymer, the object of acid value measurement, was precisely weighed and then 30 g of acetone was added to the binder polymer to uniformly dissolve it to obtain a solution. Next, an appropriate amount of phenolphthalein, an indicator, was added to the solution, and then titration was performed using a 0.1N KOH (potassium hydroxide) aqueous solution. The acid value was obtained by calculating the mass (unit: mg) of KOH required to neutralize the acetone solution of the binder polymer.

The weight average molecular weight (Mw) of the binder polymer was 35,000 and the number average molecular weight (Mn) was 16,000. The weight average molecular weight and number average molecular weight were measured by gel permeation chromatography (GPC) under the following conditions and derived by conversion using a standard polystyrene calibration curve.

(GPC conditions)

Pump: Hitachi L-6000 type (made by Hitachi Seisakusho Co., Ltd., brand name)

Columns: A total of 3 below (made by Showa Denko Materials Co., Ltd., brand name)

Gelpack GL-R440

Gelpack GL-R450

Gelpack GL-R400M

Eluent: tetrahydrofuran

Measurement temperature: 40℃

Flow rate: 2.05mL/min

Detector: Hitachi L-3300 type RI (made by Hitachi Seisakusho Co., Ltd., brand name)

<Preparation of photosensitive resin composition>

(Example 1)

100 parts by mass of a solution of the binder polymer described above (binder polymer (non-volatile matter): 56 parts by mass) and 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (EO average of 10 mol adduct, Molecular weight: 804, manufactured by Showa Denko Materials Co., Ltd., brand name: FA-321M (70)) 35 parts by mass, 2,2-bis (4- (methacryloxypolyethoxy) phenyl) propane (EO average 2.6 mol adduct, molecular weight: 478, manufactured by Kyoeisha Chemical Co., Ltd., brand name: BP-2EM, 5 parts by mass, and (PO)(EO)(PO) modified dimethacrylate (EO average of 6 mol and PO average of 12 mol) added. 4 parts by mass of water (sum value), molecular weight: 1114, manufactured by Showa Denko Materials Co., Ltd., brand name: FA-024M), and a photopolymerization initiator (2,2'-bis(o-chlorophenyl)-4,4', 6 parts by mass of 5,5'-tetraphenyl-1,2'-biimidazole, BCIM, manufactured by Hampford, 0.5 parts by mass of 5-amino-1H-tetrazole, and a hydrogen donor (Leuco Crystal Violet, LCV, Yamada) 0.5 parts by mass of a sensitizer (9,10-dibutoxyanthracene, DBA, manufactured by Kawasaki Kasei Kogyo Co., Ltd.), 0.65 parts by mass of a polymerization inhibitor A (4-t-butylcatechol, DIC) 0.015 parts by mass of polymerization inhibitor B (manufactured by Asahi Denka Kogyo Co., Ltd., brand name: LA-7RD), 0.01 part by mass of dye (malachite green, MKG, manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.) ) A photosensitive resin composition was prepared by mixing 0.02 parts by mass and 1 part by mass of additive A (light stabilizer, manufactured by Showa Denko Materials Co., Ltd., brand name: FA711MM).

(Example 2)

A photosensitive resin composition was prepared in the same manner as in Example 1, except that 0.5 parts by mass of 5-mercaptotetrazole was used instead of 0.5 parts by mass of 5-amino-1H-tetrazole.

(Comparative Example 1)

Additive B (mixture of carboxybenzotriazole, 5-amino-1H-tetrazole, and methoxypropanol; manufactured by Sanwa Kasei Co., Ltd., brand name: SF-808H) 0.5 instead of 0.5 parts by mass of 5-amino-1H-tetrazole. A photosensitive resin composition was prepared in the same manner as in Example 1 except that the mass portion was used. The content of 5-amino-1H-tetrazole in the photosensitive resin composition was 0.003 parts by mass based on a total of 100 parts by mass of the binder polymer and the photopolymerizable compound.

(Comparative Example 2)

A photosensitive resin composition was prepared in the same manner as in Example 1, except that 0.5 parts by mass of 2-mercaptobenzimidazole was used instead of 0.5 parts by mass of 5-amino-1H-tetrazole.

<Production of photosensitive elements>

A polyethylene terephthalate film (manufactured by Toray Corporation, brand name "FS-31") with a thickness of 16 μm was prepared as a support. The above-described photosensitive resin composition was applied onto a support so that the thickness was uniform, and then sequentially dried with a hot air convection dryer at 80°C and 120°C to form a photosensitive resin layer (photosensitive film, thickness after drying: 25 μm). By bonding a polyethylene film (manufactured by Tama Poly Co., Ltd., brand name "NF-15") as a protective layer to this photosensitive resin layer, a photosensitive element was obtained comprising a support, a photosensitive resin layer, and a protective layer in that order.

<Production of laminate>

A copper-clad laminate (substrate, manufactured by Showa Denko Materials Co., Ltd., brand name: MCL-E-67) having copper foil (thickness: 35 μm) disposed on both sides of a glass epoxy material was subjected to acid washing and water washing ( After washing with water, it was dried with air. Next, the copper-clad laminate is heated to 80°C, and then the copper-clad laminate, the photosensitive resin layer, and the support are formed by laminating the above-described photosensitive element so that the photosensitive resin layer is in contact with the copper surface while peeling off the protective layer. A laminate prepared in the order was obtained. Laminating was performed using a heat roll at 110°C, a compression pressure of 0.4 MPa, and a roll speed of 1.0 m/min.

<Evaluation: Adhesion>

After placing a 41-step tablet (manufactured by Showa Denko Materials Co., Ltd.) on the support of the above-mentioned laminate, a straight exposure machine (manufactured by Via Mechanics Co., Ltd., product name: DE-1UH) using a blue-violet laser diode with a wavelength of 405 nm as a light source is used. ), a drawing pattern where L/S is x/3x (x=1~20, unit: μm, 1μm interval) (area of “L/S=x/3x” and “L/S=(x+1 )/3(x+1)" area is arranged in order. Each area has a plurality of line parts and space parts, the line widths are the same and the space widths are the same), Exposure (drawing) was performed on the photosensitive resin layer through the support at an exposure amount (irradiation energy amount) such that the number of remaining stages after development of the 41-stage tablet was 15 stages.

After exposure, the support was peeled from the laminate to expose the photosensitive resin layer. Next, the unexposed portion was removed by spraying a 1.0 mass% sodium carbonate aqueous solution on the photosensitive resin layer at 30°C for twice the minimum development time. Resist judged by microscopic observation (made by Keyence Co., Ltd., product name: VHX-1000) that after development, the space portion (unexposed portion) was removed without residue, and the line portion (exposed portion) was formed without skewing or missing. The minimum value of the line width in the pattern was obtained. Next, for the line portion in the area that gives the minimum value of this line width, the line width (width of the top of the line portion) of three adjacent line portions is measured, and the average value of the line widths (unit: μm) was obtained. The results are shown in Table 1. The smaller this value means, the better the adhesion.

The above-mentioned minimum development time was evaluated in advance in the following procedure. First, the above-described laminate was cut into a rectangular shape (12.5 cm x 4 cm), and then the support was peeled off to obtain a test piece. Next, using a 1.0 mass% sodium carbonate aqueous solution at 30°C, the unexposed photosensitive resin layer in the test piece was spray developed at a pressure of 0.18 MPa, and it was visually confirmed that the unexposed photosensitive resin layer was completely removed. The shortest time was taken as the minimum development time (MD).

[Table 1]

One… photosensitive element
2… support
3, 12… photosensitive resin layer
4… protective layer
10… write
10a… insulating layer
10b, 10c... conductor layer
12a… resist pattern
14… mask
16… wiring layer
18… wiring board
L… active rays

Claims (10)

Contains a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and a tetrazole compound,
The content of monomer units of the styrene compound in the binder polymer exceeds 30% by mass,
A photosensitive resin composition in which the content of the tetrazole compound is 0.01 parts by mass or more based on a total of 100 parts by mass of the binder polymer and the photopolymerizable compound. In claim 1,
A photosensitive resin composition in which the content of the tetrazole compound is 0.01 to 1 part by mass based on a total of 100 parts by mass of the binder polymer and the photopolymerizable compound. In claim 1,
A photosensitive resin composition wherein the tetrazole compound includes 5-amino-1H-tetrazole. In claim 1,
A photosensitive resin composition in which the tetrazole compound contains 5-mercaptotetrazole. In claim 1,
A photosensitive resin composition wherein the binder polymer has a weight average molecular weight of 30,000 to 40,000. In claim 1,
A photosensitive resin composition wherein the photopolymerizable compound includes a bisphenol A type (meth)acrylic acid compound. In claim 1,
Film dealer, photosensitive resin composition. In claim 7,
A photosensitive resin composition having a thickness of 30 μm or less. Equipped with a support and a photosensitive resin layer disposed on the support,
A photosensitive element in which the photosensitive resin layer contains the photosensitive resin composition according to claim 1. A step of disposing a photosensitive resin layer on a substrate using the photosensitive resin composition according to any one of claims 1 to 8, or the photosensitive element according to claim 9,
A process of photocuring a portion of the photosensitive resin layer;
A method of manufacturing a laminate, comprising a step of removing an uncured portion of the photosensitive resin layer to form a cured product pattern.